Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0435—Rolling or calendering
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/661—Metal or alloys, e.g. alloy coatings
  • H01M4/662—Alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/665—Composites
  • H01M4/667—Composites in the form of layers, e.g. coatings
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/668—Composites of electroconductive material and synthetic resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/661—Metal or alloys, e.g. alloy coatings
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention has been made in an effort to solve the aforementioned problems of the related art and technical problems requested from the past.
• a primer coating layer including PVdF as a first binder and a conductive material and applied on a current collector;
• crystallinity of the first binder is 58 or greater.
• the second binder may be, but not limited to, the same PVdF as the first binder, and here, the second binder may have crystallinity of less than 58.
• the crystallinity which represents a weight ratio of a crystal part in the entirety of a polymer solid including the crystal part and a non-crystal part, is changed depending on a type and a structure of a polymer and varied depending on a crystallization temperature, a cooling rate, an external force, and the like.
• crystallinity of the PVdF measured by the above method is less than 58. This is because, the electrode is easily broken as the crystallinity of the PVdF is higher, and thus, if the crystallinity of the PVdF is too high, resistance is increased to cause a problem of an output, or the like.
• the inventors of the present application manufactured the electrode in which two electrode layers are formed so that a degradation of the output characteristics that may occur as the PVdF having high crystallinity is used is solved by coating a primer layer including a conductive material together with the PVdF having high crystallinity of 58 or greater on the current collector, an elongation percentage of the electrode layers is reduced to enhance safety of needle-shaped penetration, and a binder having crystallinity of less than 58 is used as a second binder together with an electrode active material in an electrode composite layer applied on the primer layer to also exhibit capacity without significantly lowering the output characteristics.
• a thickness ratio of the primer coating layer and the electrode composite layer is not particularly limited, but, since only the electrode composite layer includes an electrode active material, a thickness of the primer coating layer may be 1 to 10% with respect to a thickness of the electrode composite layer, for example, 0.1 to 5.0 ⁇ m, specifically, 0.1 to 3.0 ⁇ m.
• the thickness of the primer coating layer is less than 1% of the thickness of the electrode composite layer, the first binder is included to be too small, making it difficult to obtain the desired effect, and if the thickness of the primer coating layer exceeds 10%, the amount of the electrode composite layer including the electrode active material is relatively reduced to reduce capacity and the primer layer may act as a resistor, which is, thus, not desirable.
• the content of the first binder in the primer coating layer may be 30 to 80 wt % with respect to a total weight of the primer coating layer
• the content of the second binder in the electrode composite layer may be 1 to 15 wt % with respect to a total weight of the electrode composite layer.
• the primer coating layer is relatively close to the current collector, and thus, the primer coating layer preferably includes a relatively large content of binder as mentioned above to enhance adhesion been the current collector and the active material.
• the electrode active material may include, as a negative electrode active material, for example, at least one carbon-based material selected from the group consisting of crystalline artificial graphite, crystalline natural graphite, amorphous hard carbon, low crystalline soft carbon, carbon black, acetylene black, Ketjenblack, Super P, graphene, and fibrous carbon, Si-based material, Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1 ⁇ x Me′ y O z (Me: Mn, Fe, Pb, Ge; Me′: Al, B, P, Si, group 1, group 2, group 3 elements of the periodic table, halogen; metal composite oxide such as 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; metal oxide such as SnO, SnO 2 , PbO, PbO 2
• a filler as a component suppressing expansion of the electrode, may be selectively added to the primer coating layer and the electrode composite layer.
• the filler is not particularly limited as long as it is a fibrous material without causing a chemical change in the corresponding battery, and may be, for example, an olefin polymer such as polyethylene, polypropylene, and the like; and a fibrous material such as glass fiber and carbon fiber.
• the adhesion promoter as an auxiliary component added to enhance adhesion of the active material to the current collector, may be added in the amount of 10 wt % or less against the binder.
• the adhesion promoter may include, for example, oxalic acid, adipic acid, formic acid, an acrylic acid derivative, an itaconic acid derivative, and the like.
• the present invention further provides a method for manufacturing an electrode for a rechargeable battery according to the present invention.
• the crystallinity of the PVdF is increased as the vacuum drying temperature is increased.
• the vacuum drying temperature for the primer slurry may be a temperature higher than 130° C., which is a general electrode drying temperature, that is, 150° C. to 190° C., specifically, 160° C. to 190° C.
• the first drying of the primary slurry as a process for volatilizing NMP, may be performed for about 2 minutes to 5 minutes, and the second drying, which aims at increasing crystallinity by the PVdF, may be performed for about 12 hours to 30 hours.
• the drying temperature of the electrode composite layer may be a general electrode drying temperature similar to that of the related art, i.e., 120° C. to 140° C., and specifically, 130° C.
• the entire electrode may not have characteristics of being easily broken, and since resistance is not high, a degradation of output characteristics may be prevented.
• drying of the electrode composite layer also as a process for volatilizing NMP, may be performed for about 2 minutes to 5 minutes.
• the electrode manufacturing method according to the present invention may be changed in a partial process as necessary, and these should be interpreted to be included in coverage of the present invention. For example, rolling may be performed at a time, rather than being performed at each layer forming step.
• the electrode for a rechargeable battery according to the present invention may be used in a lithium rechargeable battery.
• the lithium rechargeable battery may have a structure in which an electrode assembly including electrodes, i.e., a positive electrode and a negative electrode and a separator interposed therebetween is filled with lithium salt-containing non-aqueous electrolyte.
• the separator is interposed between the positive electrode and the negative electrode and may be an insulating thin film having high ion permeability and mechanical strength.
• a diameter of a pore of the separator is generally 0.01 to 10 ⁇ m and a thickness thereof is generally 5 to 300 ⁇ m.
• a sheet or non-woven fabric formed of an olefin polymer such as polypropylene having chemical resistance and hydrophobic properties, glass fiber, polyethylene, or the like, is used
• the separator may be coated with a gel polymer electrolyte to enhance stability of the battery.
• Typical gel polymers include polyethyleneoxide, polyvinylidenefluoride, polyacrylonitrile, and the like.
• the solid electrolyte may also serve as the separator.
• non-aqueous organic solvent may include aprotic organic solvent such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butylolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-diosolane, 4-methyl-1,3-dioxen, diethyl ether, formamide, dimethyl formamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives,
• a lithium salt-containing non-aqueous electrolyte may be manufactured by adding lithium salt such as LiPF 6 , LiClO 4 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , and the like, to a mixture solvent of cyclic carbonate of EC or PC, as a high dielectric solvent and linear carbonate of DEC, DMC, or EMC as a low viscosity solvent.
• lithium salt such as LiPF 6 , LiClO 4 , LiBF 4 , LiN(SO 2 CF 3 ) 2
• NMP N-methyl-2-pyrrolidone
• a positive electrode was manufactured in the same manner as that of Comparative Example 1, except that the primer slurry prepared in Comparative Example 1 was applied to have a thickness of 3 ⁇ m on an aluminum foil and NMP was dried at a rate of 0.2 m/min. in a dryer under an air atmosphere having a temperature of 130° C. and dried again for 24 hours at 160° C. in a vacuum state to form a primer layer, and an active material slurry was applied to have a thickness of 150 ⁇ m on the primer layer, dried at a rate of 0.2 m/min. in a dryer having a temperature of 130° C. under an air atmosphere, and dried again for 24 hours at 160° C. in a vacuum state to form a positive electrode composite layer.
• the positive electrode of Comparative Example 4 was vacuum-dried again at 45° C. and a portion of the electrode layer was scraped out with a razor blade, and NMR of powder was measured.
• An analysis method is as follows. After measurement, areas of peaks of crystalline and non-crystalline at main peaks of the PVDFs were obtained and a percentage (%) of the area of the crystalline in the sum of the areas was calculated to obtain crystallinity.
• crystallinity was 59.7. That is, it can be seen that, when drying was performed again at 160° C. in the vacuum state, crystallinity of the PVdF was 59.7.
• the rechargeable battery manufactured according to Experimental Example 2 using the positive electrodes manufactured in Inventive Examples 1 and 2 and Comparative Examples 4 and 5 was charged to 4.2V by 0.1C and discharged to 2.5V with 0.1C during two cycles, and thereafter, it was charged to 4.2V with 0.33C and discharged to SOC 50 with 0.33C and resistance was measured for 30 seconds at SOC 50 with 3C. Results thereof are illustrated in Table 3 below.
• Comparative Example 5 including the primer layer has less increase in resistance, than Comparative Example 4 not including the primer layer.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Composite Materials (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Cell Electrode Carriers And Collectors (AREA)

Applications Claiming Priority (7)

Publications (2)

Family

ID=66678145

Family Applications (1)

Country Status (8)

Families Citing this family (3)

Citations (15)

Family Cites Families (10)

• 2018
  • 2018-11-08 KR KR1020180136861A patent/KR102609884B1/ko active IP Right Grant
  • 2018-11-09 ES ES18875665T patent/ES2928432T3/es active Active
  • 2018-11-09 HU HUE18875665A patent/HUE059987T2/hu unknown
  • 2018-11-09 PL PL18875665.4T patent/PL3582297T3/pl unknown
  • 2018-11-09 EP EP18875665.4A patent/EP3582297B1/en active Active
  • 2018-11-09 US US16/493,472 patent/US11094961B2/en active Active
  • 2018-11-09 CN CN201880019379.7A patent/CN110431691B/zh active Active
  • 2018-11-09 JP JP2019548310A patent/JP7038962B2/ja active Active

Patent Citations (20)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events